Methods and compositions relating to the hydrolysis of water-hydrolysable materials
Treatments fluids relating to the hydrolysis of water-hydrolysable materials are provided. In one embodiment, provided is a treatment fluid that comprises an aqueous liquid, a water-miscible solvent, and a water-hydrolysable material. Also provided is a hydrolysis retarder composition that comprises an aqueous liquid and a water-miscible solvent.
Latest Halliburton Energy Services, Inc. Patents:
This application is a divisional application of U.S. patent application Ser. No. 11/046,652, entitled “Methods and Compositions Relating to the Hydrolysis of Water-Hydrolysable Materials,” filed on Jan. 28, 2005, now abandoned the entire disclosure of which is incorporated herein by reference. The present invention is also related to U.S. application Ser. No. 11/046,043, entitled “Methods and Compositions Relating to the Hydrolysis of Water-Hydrolysable Materials” filed on Jan. 28, 2005, the entire disclosure of which is incorporated herein by reference.
BACKGROUNDThe present invention relates to water-hydrolysable materials and, more particularly, to treatment fluids and associated methods relating to the hydrolysis of water-hydrolysable materials.
Water-hydrolysable materials are commonly employed in subterranean operations. For instance, water-hydrolysable materials may be used in subterranean operations as fluid loss control particles, diverting agents, filter cake components, drilling fluid additives, cement additives, and the like. In some instances, the water-hydrolysable material may be in a mechanical form (e.g., plugs, sleeves, and the like). In another instance, the water-hydrolysable material may be capable of releasing a desirable degradation product, e.g., an acid, during its hydrolysis. The acid released by certain water-hydrolysable materials may be used to facilitate a reduction in viscosity of a fluid or to degrade a filter cake, as well as for numerous other functions in subterranean operations.
Inclusion of a water-hydrolysable material capable of releasing an acid in a gelled (and optionally crosslinked) treatment fluid may be used to facilitate a reduction in viscosity of such fluid. Generally, these water-hydrolysable materials likely will hydrolyze over time due to contact with water present in the fluid, thereby releasing an acid. Upon its hydrolysis, the acid will function, inter alia, to reduce the viscosity of the gelled (and optionally crosslinked) treatment fluid, for example, by breaking the crosslinks in the treatment fluid, reducing the pH of the treatment fluid sufficiently to reverse the crosslinks therein, and/or breaking down the backbone of the gelling agent present in the treatment fluid. Typically, the acid released by the water-hydrolysable materials may breakdown the gelling agents at temperatures above about 150° F.
Water-hydrolysable materials capable of releasing an acid also may be used in the degradation of acid-soluble materials present in a subterranean formation, such as those present in or adjacent to filter cakes. Filter cakes commonly may be formed by a fluid (e.g., a drill-in and servicing fluid) on the face of a portion of a subterranean formation, inter alia, to minimize damage to the permeability thereof. The filter cake often comprises an acid-soluble component (e.g., a calcium carbonate bridging agent) and a polymeric component (e.g., starch and xanthan). Before desirable fluids, such as hydrocarbons, may be produced, the filter cake generally is removed. To facilitate the degradation of the acid-soluble component, a water-hydrolysable material capable of releasing an acid may be utilized. Filter cakes also may be removed using an acid where the filter cake does not contain an acid-soluble component, for example, by degrading the underlying carbonate adjacent, if the filter cake is present in a carbonate formation.
In one instance, the filter cake may be contacted by a treatment fluid that comprises the water-hydrolysable material. The resultant acid should interact with the acid-soluble component of the filter cake and/or the underlying carbonate adjacent to the filter cake in such a way as to facilitate their degradation. In another instance, the water-hydrolysable material capable of releasing an acid may be included in the fluid (such as the drill-in and servicing fluid) that forms the filter cake, such that the filter cake further contains the water-hydrolysable material. Subsequent contact of the filter cake with an aqueous fluid hydrolyzes the water-hydrolysable material thereby releasing an acid that acts to degrade the acid soluble component of the filter cake. Among other components, the aqueous fluid may contain oxidizing agents or enzymes suitable to facilitate the degradation of the polymeric component of the filter cake.
Use of water-hydrolysable materials capable of releasing an acid may be problematic, for example, if the water-hydrolysable material hydrolyzes too slowly or too quickly. For example, where used to facilitate a reduction in viscosity of a treatment fluid, the treatment fluid may need to have a desired viscosity for a requisite duration to ensure a desirable well treatment. In some instances, as the temperature in the well bore increases, the hydrolysis rate of the water-hydrolysable material increases, which may lead to an untimely or undesired reduction in viscosity of the treatment fluid. One method used to reduce the hydrolysis rate of the water-hydrolysable material may be to encapsulate it in a slowly soluble coating that can delay the hydrolysis of the water-hydrolysable material and thus delay release of the resulting acid. However, encapsulation of the water-hydrolysable material may add undesired expense and complexity. Further, where the water-hydrolysable material has a relatively small particle size, e.g., less than about 200 microns, encapsulation may not be practicable. Also, while it is possible to “tune” the water-hydrolysable material through various methodologies (e.g., initial choice of material, choice of plasticizers, molecular weight of the material, etc.), these methods may not be sufficient to extend or decrease the degradation time appropriately and/or may not be economical.
SUMMARYThe present invention relates to water-hydrolysable materials and, more particularly, to treatment fluids and associated methods relating to the hydrolysis of water-hydrolysable materials.
In one embodiment, the present invention provides a treatment fluid that comprises an aqueous liquid, a water-miscible solvent, and a water-hydrolysable material.
In another embodiment, the present invention provides a treatment fluid that comprises an aqueous liquid, a water-miscible solvent, a water-hydrolysable material capable of releasing an acid, and a gelling agent comprising a cellulose grafted with an allyl or a vinyl monomer.
In yet another embodiment, the present invention provides a hydrolysis retarder composition that comprises an aqueous liquid and a water-miscible solvent.
The features and advantages of the present invention will be readily apparent to those skilled in the art upon a reading of the description of the specific embodiments that follows.
A more complete understanding of the present disclosure and advantages thereof may be acquired by referring to the following description taken in conjunction with the accompanying drawings, wherein:
The present invention relates to water-hydrolysable materials and, more particularly, to treatment fluids and associated methods relating to the hydrolysis of water-hydrolysable materials. The water-hydrolysable materials may be used in subterranean operations for a number of functions, including, but not limited to, fluid loss control particles, diverting agents, filter cake components, drilling fluid additives, cement additives, and the like. In some instances, the water-hydrolysable material may be in a mechanical form (e.g., plugs, sleeves, and the like). In some instances, the water-hydrolysable material may be capable of releasing a desirable degradation product, e.g., an acid, during its hydrolysis. The acid released by certain water-hydrolysable materials may be used to facilitate a reduction in viscosity of a fluid or to degrade a filter cake, as well as for numerous other functions in subterranean operations.
The treatment fluids of the present invention generally comprise an aqueous liquid and a water-miscible solvent. Among other things, because the amount of water in a treatment fluid of the present invention is reduced due to the inclusion of a water-miscible solvent therein, the hydrolysis of a water-hydrolysable material contacted by the treatment fluid or present within the treatment fluid should be at least partially delayed. For example, a hydrolysis retarder composition may comprise an aqueous liquid and a water-miscible solvent. Depending on the application, the treatment fluids of the present invention further may comprise at least one of the following: a water-hydrolysable material, a gelling agent, a crosslinking agent, or additional additives suitable for a particular application.
The aqueous liquid utilized in the treatment fluids of the present invention may be fresh water, saltwater (e.g., water containing one or more salts dissolved therein), brine (e.g., saturated saltwater), or seawater. In certain embodiments, the aqueous liquid may comprise at least one salt of potassium chloride, sodium chloride, calcium chloride, zinc chloride, potassium bromide, sodium bromide, calcium bromide, zinc bromide, sodium formate, potassium formate, or cesium formate. Among other things, the salt may be included in the aqueous liquid for density control. In some embodiments, the aqueous liquid may have a density in the range of from about 8.33 pounds per gallon (“ppg”) to about 21.5 ppg. Generally, the aqueous liquid may be from any source provided that it does not contain an excess of compounds (e.g., dissolved organics) that may adversely affect a treatment fluid of the present invention. In certain embodiments, the aqueous liquid may be present in the treatment fluids of the present invention in an amount in the range of from about 1% to about 80% by weight of the treatment fluid therein. In certain embodiments, the aqueous liquid may be present in the treatment fluids of the present invention in an amount in the range of from about 20% to about 80% by weight of the treatment fluid therein. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of water for a chosen application.
Generally, any water-miscible solvent may be used in the present invention. Among other things, inclusion of the water-miscible solvent in the treatment fluids of the present invention should act to at least partially delay the hydrolysis of a water-hydrolysable material present within or contacted by the treatment fluids of the present invention. Examples of suitable water-miscible solvents include, but are not limited to, alcohols such as methanol, glycols such as propylene glycol and ethylene glycol, ethers such as ethylene glycol monobutyl ether, esters such as propylene carbonate and ethylene glycol monomethyl acetate, derivatives thereof, and combinations thereof. Additional examples of suitable water-miscible solvents are those described in Kirk-Othmer, Fourth Edition, Volume 22, pp 536-553. Generally, the water-miscible solvent should be included in the treatment fluids of the present invention in an amount sufficient to at least partially delay the hydrolysis of the water-hydrolysable material. In some embodiments, the water-miscible solvent may be present in the treatment fluids of the present invention in an amount in the range of from about 20% to about 99% by weight of the treatment fluid. In some embodiments, the water-miscible solvent may be present in the treatment fluids of the present invention in an amount in the range of from about 20% to about 80% by weight of the treatment fluid. The amount of the water-miscible solvent to include in the treatment fluids of the present invention depends on a number of factors, including, the desired hydrolysis rate of the water-hydrolysable material, the desired density of the treatment fluid, and the hydration needs of other additives present in the treatment fluid.
A wide variety of gelling agents may be employed in the treatment fluids of the present invention. While optional, one or more gelling agents may be included in a treatment fluid of the present invention for gelling the water and increasing the treatment fluid's viscosity. Examples of suitable gelling agents include, but are not limited to, biopolymers (e.g., xanthan and succinoglycan), galactomannan gums, modified celluloses, and derivatives thereof, combinations thereof, and the like. Suitable galactomannan gums include, but are not limited to, gum arabic, gum ghatti, gum karaya, tamarind gum, tragacanth gum, guar gum, locust bean gum, and the like. Suitable galactomannan gum derivatives include, but are not limited to, guar gum derivatives, such as hydroxypropylguar (“HPG”), carboxymethylhydroxypropylguar (“CMHPG”), and carboxymethylguar (“CMG”).
Modified celluloses and derivatives thereof such as cellulose ethers, cellulose esters, and the like are also suitable for use as gelling agents in accordance with the present invention. In some embodiments, the gelling agent may be a water-soluble cellulose ether, including, but not limited to, carboxyalkylcellulose ethers such as carboxyethylcellulose and carboxymethylcellulose; mixed ethers such as carboxymethyl-hydroxyethylcellulose; hydroxyalkylcelluloses such as hydroxyethylcellulose (“HEC”) and hydroxypropylcellulose; alkylhydroxyalkylcelluloses such as methylhydroxypropylcellulose; alkylcelluloses such as methylcellulose, ethylcellulose, and propylcellulose; alkylcarboxyalkylcelluloses such as ethylcarboxymethylcellulose; alkylalkylcelluloses such as methylethylcellulose; hydroxyalkylalkylcelluloses such as hydroxypropylmethylcellulose; and the like.
In certain embodiments, the derivatized cellulose is a cellulose grafted with an allyl or a vinyl monomer, such as those disclosed in U.S. Pat. Nos. 4,982,793; 5,067,565; and 5,122,549, the relevant disclosures of which are incorporated herein by reference. The allyl or vinyl monomer should have a crosslinkable substituent, such as a vicinal dihydroxy group or a phosphonate group, which should allow the derivatized cellulose to crosslink. Examples of suitable allyl or vinyl monomers include, but are not limited to, glyceryl allyl ether (GAE), 2,3-dihydroxypropylmethacrylate (DHPM), vinyl phosphonic acid (VPA), allyl glycidyl ether (AGE), glycidyl methacrylate (GMA), and combinations thereof. In one certain embodiment, the gelling agent comprises HEC grafted with VPA. An example of a suitable gelling agent comprising HEC grafted with VPA is commercially available from Halliburton Energy Services, Inc., Duncan, Okla., as “WG-33™” gelling agent.
Where present, the gelling agent generally should be included in the treatment fluids of the present invention in an amount sufficient, among other things, to achieve the desired viscosity thereof. In some embodiments, a gelling agent may be present in the treatment fluids of the present invention in amount in the range of from about 0.25% to about 10% by weight of the treatment fluid. In other embodiments, the gelling agent may be present in the treatment fluids of the present invention in amount in the range of from about 0.75% to about 1.5% by weight of the treatment fluid.
While optional, at least a portion of the gelling agent included in the treatment fluids of the present invention may be crosslinked by a reaction comprising a crosslinking agent, e.g., to further increase the treatment fluid's viscosity thereof. Crosslinking agents typically comprise at least one metal ion that is capable of crosslinking gelling agent molecules. Examples of suitable crosslinking agents include, but are not limited to, zirconium compounds (such as, for example, zirconium lactate, zirconium lactate triethanolamine, zirconium carbonate, zirconium acetylacetonate, zirconium malate, zirconium citrate, and zirconium diisopropylamine lactate); titanium compounds (such as, for example, titanium lactate, titanium malate, titanium citrate, titanium ammonium lactate, titanium triethanolamine, and titanium acetylacetonate); aluminum compounds (such as, for example, aluminum lactate or aluminum citrate); borate compounds (such as, for example, sodium tetraborate, boric acid, disodium octaborate tetrahydrate, sodium diborate, ulexite, and colemanite); antimony compounds; chromium compounds; iron compounds; copper compounds; zinc compounds; or a combination thereof. An example of a suitable commercially available zirconium-based crosslinking agent is “CL24™” crosslinker from Halliburton Energy Services, Inc., Duncan, Okla. An example of a suitable commercially available titanium-based crosslinking agent is “CL39™” crosslinker from Halliburton Energy Services, Inc., Duncan Okla. An example of a suitable borate-based crosslinking agent is commercially available as “CL-22™” delayed borate crosslinker from Halliburton Energy Services, Inc., Duncan, Okla. Divalent ions also may be used; for example, calcium chloride and magnesium oxide. An example of a suitable divalent ion crosslinking agent is commercially available as “CL30-™” from Halliburton Energy Services, Inc., Duncan, Okla. Where present, the crosslinking agent generally should be included in the treatments fluid of the present invention in an amount sufficient, among other things, to provide the desired degree of crosslinking. In some embodiments, the crosslinking agent may be present in the treatment fluids of the present invention in an amount in the range of from about 0.01% to about 5.0% by weight of the treatment fluid.
Water-hydrolysable materials suitable for use in the present invention are those capable of degrading when contacted by water. Water-hydrolysable materials that may be used in conjunction with the present invention include, but are not limited to, degradable polymers, lactides, lactones, esters, dehydrated compounds, derivatives thereof, and combinations thereof. Those of ordinary skill in the art, with the benefit of this disclosure, will recognize other suitable water-hydrolysable materials for a particular application. Generally, the water-hydrolysable materials should degrade over time as opposed to immediately. The terms “degrading,” “degradation,” and “degradable” refer to both the relatively extreme cases of hydrolytic degradation that the degradable material may undergo, i.e., heterogeneous (or bulk erosion) and homogeneous (or surface erosion), and any stage of degradation in between these two. In some embodiments, the water-hydrolysable materials may be capable of releasing an acid upon hydrolysis. Among other things, the water-hydrolysable materials capable of releasing an acid should degrade after a desired time to release an acid, for example, to degrade a filter cake or to reduce the viscosity of a treatment fluid.
In certain embodiments, the water-hydrolysable materials comprise a degradable polymer capable of hydrolyzing when contacted by water. Suitable examples of degradable polymers that may be used in accordance with the present invention include, but are not limited to, homopolymers, random, block, graft, and star- and hyper-branched polymers. Examples of suitable degradable polymers, include, but are not limited to, polysaccharides such as dextran or cellulose; chitin; chitosan; proteins; aliphatic polyesters; poly(lactic acids); poly(glycolides); poly(ε-caprolactones); poly(hydroxybutyrates); poly(anhydrides); aliphatic polycarbonates; poly(orthoesters); poly(amino acids); poly(ethylene oxide); polyphosphazenes, polyvinyl alcohols, and copolymers and blends of any of these degradable polymers. The term “copolymer” as used herein is not limited to the combination of two polymers, but includes any combination of polymers, e.g., terpolymers and the like. Certain of these degradable polymers are capable of releasing an acid upon hydrolysis. For example, poly(lactic acids) and poly(glycolides), among others, are capable of releasing an acid upon hydrolysis.
Preferred aliphatic polyesters have the general formula of repeating units shown below:
where n is an integer between 75 and 10,000 and R is a hydrogen, alkyl, aryl, alkylaryl, acetyl, heteroatoms, or mixtures thereof. Of these aliphatic polyesters, poly(lactic acid) is preferred. Poly(lactic acid) is synthesized either from lactic acid by a condensation reaction or more commonly by ring-opening polymerization of cyclic lactide monomer. Since both lactic acid and lactide can achieve the same repeating unit, the general term poly(lactic acid) as used herein refers to formula I without any limitation as to how the polymer was made such as from lactides, lactic acid, or oligomers, and without reference to the degree of polymerization or level of plasticization. The lactide monomer exists generally in three different forms: two stereoisomers L- and D-lactide and racemic D,L-lactide (meso-lactide). The oligomers of lactic acid, and oligomers of lactide are defined by the formula:
where m is an integer 2≦m≦75. Preferably m is an integer and 2≦m≦10. These limits correspond to number average molecular weights below about 5,400 and below about 720, respectively. The chirality of the lactide units provides a means to adjust, inter alia, degradation rates, as well as physical and mechanical properties. Poly(L-lactide), for instance, is a semicrystalline polymer with a relatively slow hydrolysis rate. This could be desirable in applications of the present invention where a slower degradation of the degradable particulates is desired. Poly(D,L-lactide) may be a more amorphous polymer with a resultant faster hydrolysis rate. This may be suitable for other applications where a more rapid degradation may be appropriate. The stereoisomers of lactic acid may be used individually or combined to be used in accordance with the present invention. Additionally, they may be copolymerized with, for example, glycolide or other monomers like ε-caprolactone, 1,5-dioxepan-2-one, trimethylene carbonate, or other suitable monomers to obtain polymers with different properties or degradation times. Additionally, the lactic acid stereoisomers can be modified to be used in the present invention by, inter alia, blending, copolymerizing or otherwise mixing the stereoisomers, blending, copolymerizing or otherwise mixing high and low molecular weight poly(lactides), or by blending, copolymerizing or otherwise mixing a poly(lactic acid) with another polyester or polyesters.
One skilled in the art will recognize that plasticizers may be included in forming suitable polymeric degradable materials of the present invention. The plasticizers may be present in an amount sufficient to provide the desired characteristics, for example, more effective compatibilization of the melt blend components, improved processing characteristics during the blending and processing steps, and control and regulation of the sensitivity and degradation of the polymer by moisture.
Suitable dehydrated compounds are those materials that will degrade over time when rehydrated. For example, a particulate solid dehydrated salt or a particulate solid anhydrous borate material that degrades over time may be suitable. Specific examples of particulate solid anhydrous borate materials that may be used include but are not limited to anhydrous sodium tetraborate (also known as anhydrous borax) and anhydrous boric acid. These anhydrous borate materials are only slightly soluble in water. However, with time and heat in a subterranean environment, the anhydrous borate materials react with the surrounding aqueous fluid and are hydrated. The resulting hydrated borate materials are substantially soluble in water as compared to anhydrous borate materials and as a result degrade in the aqueous fluid.
In choosing the appropriate water-hydrolysable material, one should consider the degradation products that will result. Also, these degradation products should not adversely affect other operations or components. The choice of a water-hydrolysable material also can depend, at least in part, on the conditions of the well, e.g., well bore temperature. For instance, aliphatic polyesters have been found to be suitable for well bore temperatures in the range of 180° F. to 400° F. And, for example, lactides may be suitable for well bore temperatures less than about 180° F. Generally, lower molecular weight water-hydrolysable materials are suitable for use in lower temperature applications and higher molecular weight acid-releasing degradable materials are suitable for use in higher-temperature applications. It is within the ability of one skilled in the art, with the benefit of this disclosure, to select a suitable water-hydrolysable material.
Blends of certain water-hydrolysable materials may also be suitable. One example of a suitable blend of materials includes a blend of poly(lactic acid) and a lactide. Other materials that undergo degradation may also be suitable, if the products of the degradation do not undesirably interfere with either the subterranean treatment being performed or the subterranean formation.
The water-hydrolysable material may be included in the treatment fluids of the present invention in an amount sufficient for a particular application. For example, in embodiments where water-hydrolysable materials capable of releasing an acid are used, the water-hydrolysable material should be present in the treatment fluids of the present invention in an amount sufficient to release a desired amount of acid. In some embodiments, the amount of the released acid should be sufficient to reduce the viscosity of the treatment fluid to a desired level. In another embodiment, the amount of the released acid should be sufficient to facilitate the degradation of an acid-soluble component, for example, an acid-soluble component of a filter cake or an acid-soluble component adjacent to a filter cake. In certain embodiments, the water-hydrolysable material may be present in the treatment fluid in an amount in the range of from about 1% to about 30% by weight of the treatment fluid. In certain embodiments, the water-hydrolysable material may be present in the treatment fluid in an amount in the range of from about 3% to about 10% by weight of the treatment fluid. One of ordinary skill in the art, with the benefit of this disclosure, will be able to determine the appropriate amount of the water-hydrolysable degradable material to include in the treatment fluids of the present invention for a particular application.
The desired hydrolysis rate of the water-hydrolysable material will vary dependent on the particular application. As previously discussed, inclusion of a water-miscible solvent in the treatment fluids of the present invention should reduce the hydrolysis rate of the water-hydrolysable material. By adjusting the concentration of the water-miscible solvent in the treatment fluids of the present invention, the hydrolysis rate of the water-hydrolysable material may be controlled. One of ordinary skill in the art, with the benefit of this application, will be able to determine the appropriate hydrolysis rate of the water-hydrolysable material for a particular application.
The treatment fluids of the present invention may further comprise additional additives as deemed appropriate by one of ordinary skill in the art, with the benefit of this disclosure. Examples of such additional additives include, but are not limited to, pH-adjusting agents, pH-buffers, oxidizing agents, enzymes, lost circulation materials, scale inhibitors, surfactants, clay stabilizers, fluid loss control additives, combinations thereof, and the like.
Generally, the present invention comprises utilizing a treatment fluid of the present invention to at least partially delay the hydrolysis of a water-hydrolysable material. In one certain embodiment, the present invention provides a method of treating at least a portion of subterranean formation, the method comprising: providing a water-hydrolysable material; introducing the water-hydrolysable material into a well bore penetrating the subterranean formation; providing a treatment fluid comprising an aqueous liquid and a water-miscible solvent; introducing the treatment fluid into the well bore so as to contact the water-hydrolysable material; and allowing the water-hydrolysable material to hydrolyze. Generally, the treatment fluid may be introduced into the well bore subsequent to, or simultaneously with, the introduction of the water-hydrolysable material into the well bore. In certain embodiments, the treatment fluid may further comprise the water-hydrolysable material.
The water-hydrolysable material may be introduced into the well bore for any of a number of uses. For instance, water-hydrolysable materials may be used in subterranean operations as fluid loss control particles, diverting agents, filter cake components, drilling fluid additives, cement additives, and the like. In some embodiments, the water-hydrolysable material may be in a mechanical form (e.g., plugs, sleeves, and the like). In some instances, the water-hydrolysable material may be capable of releasing a desirable degradation product, e.g., an acid, during its hydrolysis. At a chosen time or after a desired delay period, the water-hydrolysable material should be allowed to hydrolyze so as to release an acid.
In some embodiments, the acid released by certain water-hydrolysable materials may be used to degrade acid-soluble components present in the subterranean formation. In some embodiments, the acid-soluble component may be present in or adjacent to a filter cake in the subterranean formation. In another embodiment, the acid-soluble component may be other acid-soluble damage present in the subterranean formation (e.g., in the near well bore region). In some embodiments, the water-hydrolysable material is present in the treatment fluid. In other embodiments, the water-hydrolysable material is present in a filter cake that is present in the subterranean formation. For example, the water-hydrolysable material may be introduced into the formation as part of the fluid that forms the filter cake, such that the filter cake contains the water-hydrolysable material. As those of ordinary skill in the art will appreciate, the treatment fluid may need to be shut in for a period of time to allow for the desired amount of acid to be released.
In some embodiments, the acid released by certain water-hydrolysable materials may be used to facilitate a reduction in viscosity of the treatment fluid, for example, wherein the treatment fluid comprises a gelling agent. As previously discussed, at least a portion of the gelling agent may be crosslinked by a reaction comprising a crosslinking agent. The treatment fluid may be recovered from the well bore subsequent to its reduction in viscosity. Where used to facilitate a reduction in viscosity of a treatment fluid, the treatment operation may be any of a variety of subterranean treatments employed in subterranean operations where a viscosified fluid may be used, including, fracturing, gravel packing, chemical diversions, and fluid loss control treatments.
For example, in one certain embodiment, the present invention provides a method of completing a well comprising providing a treatment fluid of the present invention that comprises an aqueous liquid, a water-miscible solvent, a water-hydrolysable material capable of releasing an acid, and a gelling agent; and introducing the treatment fluid of the present invention into a well bore in an amount sufficient to fill a portion of the well bore within a permeable section of a subterranean formation. As previously discussed, at least a portion of the gelling agent may be crosslinked by a reaction comprising a crosslinking agent. As those of ordinary skill in the art will appreciate, with the benefit of this disclosure, the treatment fluids of the present invention further may comprise other additives suitable for a particular application. Generally, in these embodiments, the treatment fluid of the present invention should have sufficient rigidity to resist entry into the permeable section of the subterranean formation. Subsequent to placement of the treatment fluid of the present invention into the portion of the well bore, a high-density completion fluid may be placed into the well bore behind the treatment fluid. In some embodiments, the treatment fluid may have about the same density as the high-density treatment fluid. Among other things, the treatment fluid of the present invention should block the high-density completion fluid from being lost or entering the permeable section of the subterranean formation. Furthermore, the total hydrostatic pressure exerted onto the subterranean formation by the high-density completion fluid plus the treatment fluid of the present invention should be sufficient to provide well control. At a chosen time or after a desired delay period, the water-hydrolysable material should be allowed to hydrolyze so as to release an acid that facilitates a reduction in the treatments fluid's viscosity. The treatment fluid may be recovered from the well bore subsequent to its reduction in viscosity.
To facilitate a better understanding of the present invention, the following example of specific embodiments is given. In no way should the following examples be read to limit, or define, the scope of the invention.
EXAMPLETests were performed on samples of various fluids in order to compare the relative break times of the fluids. Sample Fluid No. 1 was a crosslinked treatment fluid that was prepared without the addition of a water-miscible solvent. Sample Fluid No. 2 was a crosslinked treatment fluid that comprised propylene glycol. The tests were performed at 195° F. in a Fann HPHT Filter Press according to the steps listed in Table 1 below.
Sample Fluid No. 1 was prepared by pouring 500 ml of an 11.6 ppg calcium chloride brine into a Waring blender while mixing. Next, 21.55 ml of WG-33™ gelling agent were added to the blender while mixing. Thereafter, 2.5 ml of 20° Be hydrochloric acid were added to the blender while mixing. The resulting solution was mixed for 5 additional minutes, and the solution was then allowed to hydrate for about 1 hour. After the 1-hour hydration period, 200 ml of the above-prepared solution was used for the remainder of this test. Next, 7 grams of 18/20 mesh particulate poly(lactic acid) was added to the 200 ml of the solution. Thereafter, 0.72 grams of CL-30™ crosslinker were added to the blender while mixing. The resultant solution was emptied into a jar and remained static at room temperature for 1 hour to ensure crosslinking.
After the 1-hour waiting period, Sample Fluid No. 1 was placed into the HPHT cell using a 35-micron disc with a piston on top. The results from this test are illustrated in
Sample Fluid No. 2 was prepared by pouring 220.5 ml of propylene glycol into a Waring blender while mixing. Next, 13.5 ml of WG-33™ gelling agent were added to the blender while mixing. The resulting solution was mixed for 5 minutes. Thereafter, 1.6 ml of 20° Be hydrochloric acid were added to the blender while mixing. Next, 94.5 ml of an 11.6 ppg calcium chloride brine was added to the blender while mixing. The resulting solution was mixed for 5 additional minutes, and the solution was then allowed to hydrate for about 1 hour. After the 1-hour hydration period, 200 ml of the above-prepared solution was used for the remainder of this test. Next, 7 grams of 18/20 mesh particulate poly(lactic acid) was added to the 200 ml of the solution. Thereafter, 0.72 grams of CL-30™ crosslinker were added to the blender while mixing. The resultant solution was emptied into a jar and remained static at room temperature for 1 hour to ensure crosslinking.
After the 1-hour waiting period, Sample Fluid No. 2 was placed into the HPHT cell using a 35 micron disc with a piston on top. The results from this test are illustrated in
Therefore, this example shows that the inclusion of a water-miscible solvent in the treatment fluids of the present invention may control the hydrolysis rate of a water-hydrolysable material included therein.
Therefore, the present invention is well adapted to carry out the objects and attain the ends and advantages mentioned as well as those which are inherent therein. While numerous changes may be made by those skilled in the art, such changes are encompassed within the spirit of this invention as defined by the appended claims.
Claims
1. A treatment fluid comprising:
- an aqueous liquid;
- propylene carbonate in an amount of from about 20% to about 99% by weight of the treatment fluid;
- a gelling agent selected from the group consisting of a galactomannan gum, a modified cellulose, and any combination thereof; and,
- about 1% to about 30% by weight of a mixture of anhydrous borate and an ester, wherein the ester is selected from the group consisting of a poly(lactic acid), a poly(glycolide), a poly(ε-caprolactone), a poly(hydroxybutyrate), a poly(orthoester), a blend of poly(lactic acid) and a lactide, any copolymer thereof and any combination thereof.
2. The treatment fluid of claim 1 wherein the gelling agent comprises a cellulose grafted with an allyl or a vinyl monomer.
3. The treatment fluid of claim 1 wherein at least a portion of the gelling agent is crosslinked.
4. The treatment fluid of claim 1 wherein the propylene carbonate is present in an amount of from about 20% to about 80% by weight of the treatment fluid.
5. The treatment fluid of claim 1 wherein the mixture is present in an amount of from about 3% to about 10% by weight of the treatment fluid.
6. The treatment fluid of claim 1 wherein the mixture is capable of releasing an acid.
7. The treatment fluid of claim 1 wherein the mixture comprises a poly(lactic acid).
8. The treatment fluid of claim 1 wherein the treatment fluid further comprises at least one of the following: a polysaccharide; a chitin; a chitosan; a protein; an aliphatic polycarbonate; a poly(amino acid); a poly(ethylene oxide); a polyphosphazene; a polyvinyl alcohol; any copolymer thereof; and any combination thereof.
9. The treatment fluid of claim 1 wherein the ester comprises a blend of poly(lactic acid) and a lactide.
10. A treatment fluid comprising:
- an aqueous liquid;
- propylene carbonate in an amount from about 20% to about 99% by weight of the treatment fluid;
- about 1% to about 30% by weight of the treatment fluid of a mixture of anhydrous borate and an ester, wherein the ester is selected from the group consisting of a poly(lactic acid), a poly(glycolide), a poly(ε-caprolactone), a poly(hydroxybutyrate), a poly(orthoester), any copolymer thereof, and any combination thereof; and
- a gelling agent in an amount from about 0.25% to about 10% by weight of the treatment fluid, wherein the gelling agent is selected from the group consisting of a galactomannan gum, a modified cellulose and any combination thereof.
11. The treatment fluid of claim 10 wherein at least a portion of the gelling agent is crosslinked.
12. The treatment fluid of claim 10 wherein the gelling agent comprises a cellulose grafted with an allyl or a vinyl monomer.
13. The treatment fluid of claim 10 wherein the propylene carbonate is present in an amount of from about 20% to about 80% by weight of the treatment fluid.
14. The treatment fluid of claim 10 wherein the mixture is present in an amount of from about 3% to about 10% by weight of the treatment fluid.
2238671 | April 1941 | Woodhouse |
2703316 | March 1955 | Schneider |
3173484 | March 1965 | Huitt |
3195635 | July 1965 | Fast |
3272650 | September 1966 | MacVittie |
3302719 | February 1967 | Fischer |
3364995 | January 1968 | Atkins et al. |
3366178 | January 1968 | Malone et al. |
3455390 | July 1969 | Gallus |
3784585 | January 1974 | Schmitt et al. |
3806465 | April 1974 | Karl et al. |
3819525 | June 1974 | Hattenbrun |
3828854 | August 1974 | Templeton et al. |
3868998 | March 1975 | Lybarger et al. |
3912692 | October 1975 | Casey et al. |
3948672 | April 6, 1976 | Harnsberger |
3955993 | May 11, 1976 | Curtice et al. |
3960736 | June 1, 1976 | Free et al. |
3968840 | July 13, 1976 | Tate |
3998272 | December 21, 1976 | Maly |
3998744 | December 21, 1976 | Arnold et al. |
4068718 | January 17, 1978 | Cooke, Jr. et al. |
4169798 | October 2, 1979 | DeMartino |
4172066 | October 23, 1979 | Zweigle et al. |
4261421 | April 14, 1981 | Watanabe |
4387769 | June 14, 1983 | Erbstoesser et al. |
4392964 | July 12, 1983 | House et al. |
4460052 | July 17, 1984 | Gockel |
4470915 | September 11, 1984 | Conway |
4498995 | February 12, 1985 | Gockel |
4521316 | June 4, 1985 | Sikorski |
4526695 | July 2, 1985 | Erbstoesser et al. |
4694905 | September 22, 1987 | Armbruster |
4715967 | December 29, 1987 | Bellis et al. |
4716964 | January 5, 1988 | Erbstoesser et al. |
4772346 | September 20, 1988 | Anderson et al. |
4785884 | November 22, 1988 | Armbruster |
4793416 | December 27, 1988 | Mitchell |
4797262 | January 10, 1989 | Dewitz |
4809783 | March 7, 1989 | Hollenbeck et al. |
4817721 | April 4, 1989 | Pober |
4843118 | June 27, 1989 | Lai et al. |
4848467 | July 18, 1989 | Cantu et al. |
4886354 | December 12, 1989 | Welch et al. |
4957165 | September 18, 1990 | Cantu et al. |
4961466 | October 9, 1990 | Himes et al. |
4982793 | January 8, 1991 | Holtmyer et al. |
4986353 | January 22, 1991 | Clark et al. |
4986354 | January 22, 1991 | Cantu et al. |
4986355 | January 22, 1991 | Casad et al. |
5067565 | November 26, 1991 | Holtmyer et al. |
5082056 | January 21, 1992 | Tackett, Jr. |
5122549 | June 16, 1992 | Holtmyer et al. |
5142023 | August 25, 1992 | Gruber et al. |
5216050 | June 1, 1993 | Sinclair |
5247059 | September 21, 1993 | Gruber et al. |
5249628 | October 5, 1993 | Surjaatmadia |
5295542 | March 22, 1994 | Cole et al. |
5304620 | April 19, 1994 | Holtmyer et al. |
5325923 | July 5, 1994 | Surjaatmadja et al. |
5330005 | July 19, 1994 | Card et al. |
5359026 | October 25, 1994 | Gruber |
5360068 | November 1, 1994 | Sprunt et al. |
5363916 | November 15, 1994 | Himes et al. |
5373901 | December 20, 1994 | Norman et al. |
5386874 | February 7, 1995 | Laramay et al. |
5396957 | March 14, 1995 | Surjaatmadja et al. |
5402846 | April 4, 1995 | Jennings, Jr. et al. |
5439055 | August 8, 1995 | Card et al. |
5460226 | October 24, 1995 | Lawson et al. |
5464060 | November 7, 1995 | Hale et al. |
5475080 | December 12, 1995 | Gruber et al. |
5484881 | January 16, 1996 | Gruber et al. |
5497830 | March 12, 1996 | Boles et al. |
5499678 | March 19, 1996 | Surjaatmadja et al. |
5505787 | April 9, 1996 | Yamaguchi |
5512071 | April 30, 1996 | Yam et al. |
5521242 | May 28, 1996 | Supcoe et al. |
5536807 | July 16, 1996 | Gruber et al. |
5591700 | January 7, 1997 | Harris et al. |
5594095 | January 14, 1997 | Gruber et al. |
5604186 | February 18, 1997 | Hunt et al. |
5607905 | March 4, 1997 | Dobson, Jr. et al. |
5670473 | September 23, 1997 | Scepanski |
5698322 | December 16, 1997 | Tsai et al. |
5765642 | June 16, 1998 | Surjaatmadja |
5783205 | July 21, 1998 | Berggren et al. |
5791415 | August 11, 1998 | Nguyen et al. |
5833000 | November 10, 1998 | Weaver et al. |
5849401 | December 15, 1998 | El-Afandi et al. |
5853048 | December 29, 1998 | Weaver et al. |
5893416 | April 13, 1999 | Read |
5908073 | June 1, 1999 | Nguyen et al. |
5924488 | July 20, 1999 | Nguyen et al. |
5964291 | October 12, 1999 | Bourne et al. |
5996694 | December 7, 1999 | Dewprashad et al. |
6004400 | December 21, 1999 | Bishop et al. |
6024170 | February 15, 2000 | McCabe et al. |
6028113 | February 22, 2000 | Scepanski |
6047772 | April 11, 2000 | Weaver et al. |
6114410 | September 5, 2000 | Betzold |
6123965 | September 26, 2000 | Jacob et al. |
6131661 | October 17, 2000 | Conner et al. |
6135987 | October 24, 2000 | Tsai et al. |
6143698 | November 7, 2000 | Murphey et al. |
6162766 | December 19, 2000 | Muir et al. |
6169058 | January 2, 2001 | Le et al. |
6172011 | January 9, 2001 | Card et al. |
6189615 | February 20, 2001 | Sydansk |
6202751 | March 20, 2001 | Chatterji et al. |
6209643 | April 3, 2001 | Nguyen et al. |
6209646 | April 3, 2001 | Reddy et al. |
6214773 | April 10, 2001 | Harris et al. |
6242390 | June 5, 2001 | Mitchell et al. |
6260622 | July 17, 2001 | Blok et al. |
6311773 | November 6, 2001 | Todd et al. |
6323307 | November 27, 2001 | Bigg et al. |
6326458 | December 4, 2001 | Gruber et al. |
6328105 | December 11, 2001 | Betzold |
6357527 | March 19, 2002 | Norman et al. |
6364945 | April 2, 2002 | Chatterji et al. |
6380138 | April 30, 2002 | Ischy et al. |
6387986 | May 14, 2002 | Moradi-Araghi et al. |
6390195 | May 21, 2002 | Nguyen et al. |
6394185 | May 28, 2002 | Constien |
6422314 | July 23, 2002 | Todd et al. |
6454003 | September 24, 2002 | Chang et al. |
6485947 | November 26, 2002 | Rajgarhia et al. |
6488763 | December 3, 2002 | Brothers et al. |
6494263 | December 17, 2002 | Todd |
6508305 | January 21, 2003 | Brannon et al. |
6509301 | January 21, 2003 | Vollmer |
6527051 | March 4, 2003 | Reddy et al. |
6554071 | April 29, 2003 | Reddy et al. |
6569814 | May 27, 2003 | Brady et al. |
6599863 | July 29, 2003 | Palmer et al. |
6667279 | December 23, 2003 | Hessert et al. |
6669771 | December 30, 2003 | Tokiwa et al. |
6681856 | January 27, 2004 | Chatterji et al. |
6686328 | February 3, 2004 | Binder |
6702023 | March 9, 2004 | Harris et al. |
6710019 | March 23, 2004 | Sawdon et al. |
6761218 | July 13, 2004 | Nguyen et al. |
6763888 | July 20, 2004 | Harris et al. |
6793018 | September 21, 2004 | Dawson et al. |
6817414 | November 16, 2004 | Lee |
6837309 | January 4, 2005 | Boney et al. |
6840318 | January 11, 2005 | Lee et al. |
6852173 | February 8, 2005 | Banerjee et al. |
6861394 | March 1, 2005 | Ballard et al. |
6886635 | May 3, 2005 | Hossaini et al. |
6896058 | May 24, 2005 | Munoz, Jr. et al. |
6949491 | September 27, 2005 | Cooke, Jr. |
6983801 | January 10, 2006 | Dawson et al. |
6997259 | February 14, 2006 | Nguyen |
7000701 | February 21, 2006 | Todd et al. |
7021377 | April 4, 2006 | Todd et al. |
7032663 | April 25, 2006 | Nguyen |
7036586 | May 2, 2006 | Roddy et al. |
7036587 | May 2, 2006 | Munoz, Jr. et al. |
7044220 | May 16, 2006 | Nguyen et al. |
7044224 | May 16, 2006 | Nguyen |
7049272 | May 23, 2006 | Sinclair et al. |
7063151 | June 20, 2006 | Nguyen et al. |
7066258 | June 27, 2006 | Justus et al. |
7066260 | June 27, 2006 | Sullivan et al. |
7080688 | July 25, 2006 | Todd et al. |
7093664 | August 22, 2006 | Todd et al. |
7096947 | August 29, 2006 | Todd et al. |
7131491 | November 7, 2006 | Blauch et al. |
7132389 | November 7, 2006 | Lee |
7140438 | November 28, 2006 | Frost et al. |
7156174 | January 2, 2007 | Roddy et al. |
7168489 | January 30, 2007 | Frost et al. |
7172022 | February 6, 2007 | Reddy et al. |
7178596 | February 20, 2007 | Blauch et al. |
7195068 | March 27, 2007 | Todd |
7204312 | April 17, 2007 | Roddy et al. |
7205264 | April 17, 2007 | Boles |
7219731 | May 22, 2007 | Sullivan et al. |
7261156 | August 28, 2007 | Nguyen et al. |
7264051 | September 4, 2007 | Nguyen et al. |
7265079 | September 4, 2007 | Willberg et al. |
7276466 | October 2, 2007 | Todd et al. |
7299869 | November 27, 2007 | Kalman |
7299876 | November 27, 2007 | Lord et al. |
7306037 | December 11, 2007 | Nguyen et al. |
7353876 | April 8, 2008 | Savery et al. |
7353879 | April 8, 2008 | Todd et al. |
7413017 | August 19, 2008 | Nguyen et al. |
7419937 | September 2, 2008 | Rimmer et al. |
7448450 | November 11, 2008 | Luke et al. |
7455112 | November 25, 2008 | Moorehead et al. |
7461697 | December 9, 2008 | Todd et al. |
7475728 | January 13, 2009 | Pauls et al. |
7476644 | January 13, 2009 | Cooke, Jr. |
7484564 | February 3, 2009 | Welton et al. |
7497258 | March 3, 2009 | Savery et al. |
7497278 | March 3, 2009 | Schriener et al. |
7506689 | March 24, 2009 | Surjaatmadja et al. |
7547665 | June 16, 2009 | Welton et al. |
7553800 | June 30, 2009 | Munoz, Jr. |
7595280 | September 29, 2009 | Welton et al. |
7598208 | October 6, 2009 | Todd |
7608566 | October 27, 2009 | Saini et al. |
7608567 | October 27, 2009 | Saini |
7648946 | January 19, 2010 | Munoz, Jr. |
7829507 | November 9, 2010 | Todd et al. |
20010016562 | August 23, 2001 | Muir et al. |
20030130133 | July 10, 2003 | Vollmer |
20030181532 | September 25, 2003 | Parris et al. |
20030220203 | November 27, 2003 | Harris et al. |
20040072700 | April 15, 2004 | Gupta et al. |
20040138070 | July 15, 2004 | Jones et al. |
20040152601 | August 5, 2004 | Still et al. |
20040231845 | November 25, 2004 | Cooke, Jr. |
20050028976 | February 10, 2005 | Nguyen |
20050034861 | February 17, 2005 | Saini et al. |
20050059556 | March 17, 2005 | Munoz, Jr. et al. |
20050113264 | May 26, 2005 | Vollmer |
20050126785 | June 16, 2005 | Todd |
20050183741 | August 25, 2005 | Surjaatmadja et al. |
20050277554 | December 15, 2005 | Blauch et al. |
20060032633 | February 16, 2006 | Nguyen |
20060046938 | March 2, 2006 | Harris et al. |
20060105917 | May 18, 2006 | Munoz, Jr. |
20060169182 | August 3, 2006 | Todd et al. |
20060169448 | August 3, 2006 | Savery et al. |
20060169452 | August 3, 2006 | Savery et al. |
20060169453 | August 3, 2006 | Savery et al. |
20060172893 | August 3, 2006 | Todd et al. |
20060205608 | September 14, 2006 | Todd |
20060243449 | November 2, 2006 | Welton et al. |
20060247135 | November 2, 2006 | Welton et al. |
20060254774 | November 16, 2006 | Saini et al. |
20060283597 | December 21, 2006 | Schriener et al. |
20070042912 | February 22, 2007 | Welton et al. |
20070049501 | March 1, 2007 | Saini et al. |
20070066492 | March 22, 2007 | Funkhouser et al. |
20070066493 | March 22, 2007 | Funkhouser et al. |
20070078063 | April 5, 2007 | Munoz, Jr. |
20070078064 | April 5, 2007 | Munoz et al. |
20070238623 | October 11, 2007 | Saini et al. |
20070281868 | December 6, 2007 | Pauls et al. |
20080026955 | January 31, 2008 | Munoz et al. |
20080026959 | January 31, 2008 | Munoz et al. |
20080026960 | January 31, 2008 | Munoz et al. |
20080027157 | January 31, 2008 | Munoz et al. |
20080070810 | March 20, 2008 | Mang |
20080139415 | June 12, 2008 | Todd et al. |
20080169102 | July 17, 2008 | Carbajal et al. |
20090062157 | March 5, 2009 | Munoz et al. |
20090258798 | October 15, 2009 | Munoz |
2 491 934 | January 2004 | CA |
2 560 938 | October 2005 | CA |
0 510 762 | October 1992 | EP |
0 879 935 | November 1998 | EP |
0 879 935 | November 1998 | EP |
1 413 710 | April 2004 | EP |
2412389 | September 2005 | GB |
2004181820 | July 2004 | JP |
WO 93/15127 | August 1993 | WO |
WO 94/07949 | April 1994 | WO |
WO 94/08078 | April 1994 | WO |
WO 94/08090 | April 1994 | WO |
WO 95/09879 | April 1995 | WO |
WO 97/11845 | April 1997 | WO |
WO 99/27229 | June 1999 | WO |
WO 00/57022 | September 2000 | WO |
WO 01/02698 | January 2001 | WO |
WO 01/87797 | November 2001 | WO |
WO 02/12674 | February 2002 | WO |
WO02/055843 | July 2002 | WO |
WO 03/027431 | April 2003 | WO |
WO 03/027431 | April 2003 | WO |
WO 2004/007905 | January 2004 | WO |
WO 2004/037946 | May 2004 | WO |
WO 2004/038176 | May 2004 | WO |
- Office Action for U.S. Appl. No. 11/046,043 dated Jul. 26, 2007.
- Office Action for U.S. Appl. No. 11/046,043 dated Nov. 2, 2007.
- Office Action for U.S. Appl. No. 11/046,043 dated Jan. 14, 2008.
- NatureWorks Product Bulletin entitled NatureWorks PLA Polymer 3001D, Injection Molding Process Guide, 2005.
- NatureWorks Product Bulletin entitled NatureWorks PLA Polymer 4060D, for Heat Seal Layer in Coextruded Oriented Films, 2005.
- NatureWorks article entitled NatureWorks, Crystallizing and Drying of PLA, 2005.
- Skrabal et al., The Hydrolysis Rate of Orthoformic Acid Ethyl Ether, Chemical Institute of the University of Graz, pp. 1-38, 1921.
- Heller, et al., Poly(ortho esters)—From Concept to Reality, Biomacromolecules, vol. 5, No. 5, pp. 1625-1632, 2004.
- Schwach-Abdellaoui, et al., Hydrolysis and Erosion Studies of Autocatalyzed Poly(ortho esters) Containing Lactoyl Lactyl Acid Dimers, American Chemical Society, vol. 32, No. 2, pp. 301-307, 1999.
- Ng, et al., Synthesis and Erosion Studies of Self-Catalyzed Poly(ortho ester)s, American Chemical Society, vol. 30, No. 4, pp. 770-772, 1997.
- Ng, et al., Development of a Poly(ortho ester) Prototype With a Latent Acid in the Polymer Backbone for 5-Fluorouracil Delivery, Journal of Controlled Release 65, pp. 367-374, 2000.
- Rothen-Weinhold, et al., Release of BSA from Poly(ortho ester) Extruded Thin Strands, Journal of Controlled Release, 71, pp. 31-37, 2001.
- Heller, et al., Poly(ortho ester)s—Their Development and Some Recent Applications, European Journal of Pharmaceutics and Biopharmaceutics, 50, pp. 121-128, 2000.
- Heller, et al., Poly(ortho esters); Synthesis, Characterization, Properties and Uses, Advanced Drug Delivery Reviews, 54, pp. 1015-1039, 2002.
- Heller, et al., Poly(ortho esters) for the Pulsed and Continuous Delivery of Peptides and Proteins, Controlled Release and Biomedical Polymers Department, SRI International, pp. 39-56, not dated.
- Zignani, et al., Subconjunctival Biocompatibility of a Viscous Bioerodable Poly(ortho ester), J. Biomed Mater Res., 39, pp. 277-285, 1998.
- Toncheva, et al., Use of Block Copolymers of Poly(Ortho Esters) and Poly(Ethylene Glycol), Journal of Drug Targeting, vol. 11(6), pp. 345-353, 2003.
- Schwach-Abdellaoui, et al., Control of Molecular Weight for Auto-Catalyzed Poly(ortho ester) Obtained by Polycondensation Reaction, International Journal of Polymer Anal. Charact., 7:145-161, pp. 145-161, 2002.
- Heller, et al., Release of Norethindrone from Poly(Ortho Esters), Polymer Engineering and Science, vol. 21, No. 11, pp. 727-731, 1981.
- Simmons, et al., Poly(phenyllactide): Synthesis, Characterization, and Hydrolytic Degradation, Biomacromolecules, vol. 2, No. 2, pp. 658-663, 2001.
- Yin, et al., Preparation and Characterization of Substituted Polylactides, American Chemical Society, vol. 32, No. 23, pp. 7711-7718, 1999.
- Yin, et al., Synthesis and Properties of Polymers Derived from Substituted Lactic Acids, American Chemical Society, Ch. 12, pp. 147-159, 2001.
- Cantu, et al., Laboratory and Field Evaluation of a Combined Fluid-Loss-Control Additive and Gel Breaker for Fracturing Fluids, SPE 18211, Society of Petroleum Engineers, 1990.
- Love, et al., Selectively Placing Many Fractures in Openhole Horizontal Wells Improves Production, SPE 50422, Society of Petroleum Engineers, 1998.
- McDaniel, et al., Evolving New Stimulation Process Proves Highly Effective in Level 1 Dual-Lateral Completion, SPE 78697, Society of Petroleum Engineers, 2002.
- Albertsson, et al., Aliphatic Polyesters: Synthesis, Properties and Applications, Advances in Polymer Science, vol. 157, Degradable Aliphatic Polyesters, 2002.
- Dechy-Cabaret, et al., Controlled Ring-Opening Polymerization of Lactide and Glycolide, American Chemical Society, Chemical Reviews, A-Z, AA-AD, received 2004.
- Funkhouser, et al., Synthetic Polymer Fracturing Fluid for High-Temperature Applications, SPE 80236, Society of Petroleum Engineers, 2003.
- Chelating Agents, Encyclopedia of Chemical Technology, vol. 5, pp. 764-795, not dated.
- Vichaibun, et al., A New Assay for the Enzymatic Degradation of Polylactic Acid, Short Report, ScienceAsia, vol. 29, pp. 297-300, 2003.
- Halliburton, SurgiFracSM Service, A Quick and Cost-Effective Method to Help Boost Production from Openhole Horizontal Completions, Halliburton Communications, HO 3297, 2002.
- Halliburton, Cobra FracSM Service, Coiled Tubing Fracturing—Cost-Effective Method for Stimulating Untapped Reserves, HO 2319R, Halliburton Energy Services, 2002.
- Halliburton, CobraJet FracSM Service, Cost-Effective Technology That Can Help Reduce Cost Per Boe Produced, Shorten Cycle Time and Reduce Capex, Halliburton Communications, 2000.
- Y. Chiang, et al., Hydrolysis of Ortho Esters: Further Investigation of the Factors Which Control the Rate-Determining Step, Engineering Information Inc., NY, NY, vol. 105, No. 23, (XP-002322842), 1983.
- M. Ahmand, et al., Ortho Ester Hydrolysis: Direct Evidence for a Three-Stage Reaction Mechanism, Engineering Information Inc., NY, NY, vol. 101, No. 10, (XP-002322843), 1979.
- Cordes, et al., Mechanism and Catalysis for Hydrolysis of Acetals, Ketals, and Other Esters, Department of Chemistry, Indiana University, Blomington, Indiana, Chemical Reviews, vol. 74, No. 5, pp. 581-603, 1974.
- Todd, et al., A Chemical “Trigger” Useful for Oilfield Applications, Society of Petroleum Engineers, Inc., SPE 92709, 2005.
- Office Action for U.S. Appl. No. 11/046,652 dated Oct. 2, 2007.
- Office Action for U.S. Appl. No. 11/046,652 dated Sep. 4, 2008.
- Office Action for U.S. Appl. No. 11/046,652 dated Dec. 14, 2009.
- Office Action for U.S. Appl. No. 11/046,043 dated Dec. 16, 2010.
- Office Action for U.S. Appl. No. 11/046,043 dated Apr. 7, 2011.
Type: Grant
Filed: Apr 14, 2010
Date of Patent: Oct 4, 2011
Patent Publication Number: 20100197527
Assignee: Halliburton Energy Services, Inc. (Duncan, OK)
Inventors: Bradley L. Todd (Duncan, OK), Karen Savery (Duncan, OK)
Primary Examiner: Alicia Toscano
Attorney: McDermott Will & Emery LLP
Application Number: 12/760,385
International Classification: E21B 43/00 (20060101);